ELECTROCHEMICAL-BEHAVIOR OF TRANS-[FEH(CNR)(DPPE)2]+ - KINETIC-PARAMETERS DETERMINED BY DIGITAL-SIMULATION OF CYCLIC VOLTAMMETRY

A new digital simulation program, based on the box method, has been developed and applied to the cyclic voltammetric ECECE anodic behaviour of trans-[FeH(CNR)(dppe)2]+ (R = Me, Et, (t)Bu, C6H4Me-4, C6H4NO2-4, or C6H4OMe-4; dppe = Ph2PCH2CH2PPh2), allowing us to estimate relevant kinetic parameters, in particular the homogeneous rate constant for electroinduced proton loss upon metal-hydride bond cleavage. This is shown to correlate with the electron donor/acceptor properties of the trans isocyanide ligand, as expressed by the electrochemical P(L) ligand parameter, and the Taft sigma* polar constant (for the alkyl isocyanides) or the Hammett sigma(p)+ constant (for the aromatic isocyanides).